Thiophosphate acetyl hydrazines

ABSTRACT

ORGANOPHOSPHOROUS COMPOUNDS REPRESENTED BY THE FOLLOWING STRUCTURE:   R-P(=X)(-R1)-S-(C(-R2)(-R3))N-C(=X)-N(-R4)-N(-R5)-R6   WHEREIN R AND R1 MAY OR MAY NOT BE THE SAME AND ARE SELECTED FROM THE GROUP CONSISTING OF C1-C6 ALKOXY OR ALKYL, C1-C6 ALKOXYALKYL, PHENOXY OPTIONALLY SUBSTITUTED BY HALOGEN, NITRO OR C1-C6 ALKYL, PHENYLTHIO OPTIONALLY SUBSTITUTED BY HALOGEN, NITRO OR C1-C6 ALKYL, C1-C6 ALKYLTHIO, BRANCHED AND UNBRANCHED, PHENYL OPTIONALLY SUBSTITUTED BY HALOGEN, NITRO OR C1-C6 ALKYL, R2, R3 AND R4 MAY OR MAY NOT BE THE SAME AND ARE SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, C1-C6 ALKYL, UNSSUBSTITUTED, BRANCHED OR UNBRANCHED OR OPTIONALLY SUBSTITUTED BY HALOGEN, C1-C6 ALKOXY, C1-C6 ALKYLTHIO, C1-C6 ALKLTHIOALKYL, C1-C6 ALKOXY ALKYL OR MONO AND DIALKYLAMINOALKYL, PHENYL OPTIONALLY SUBSTITUTED BY HALOGEN, NITRO OR C1-C6 ALKYL, X IS EITHER O OR S AND N IS AN INTEGER RANGING FROM 1-3, R5 AND R6 MAY BE THE SAME OR DIFFERENT AND ARE SELECTED FROM THE GROUP CONSISTING OF   -(C(-R2)(-R3))A-Z, -(C(-R2)(-R3))A-L-(C(-R2)(-R3))-H,   -Y-A   SUBSTITUTED OR UNSUBSTITUTED ARYL AND HETEROARYL, WHEREIN Z=CN, COOR2, CON(R2)2, NO2, SO2N(R2)2, COOH, TRIHALOALKYL,   O=CH-, O=C(-R2)-   WHEREIN L=O, S, SO, SO2, NH, NR2,   -CO-, -C(=S)-, -C(=N-R2)-, Y=C=O, -C(=S)-   SO, SO2, A=OR2, SR2, NHR2, N(R2)2 AND A IS AN INTEGER RANGING FROM 1 TO 6, WITH THE PROVISO THAT WHEN R5 IS THE SAME AS R2, THEN R6 CANNOT BE R2 EXCEPT WHEN R5 OR R6 IS ARYL OR HETEROARYL.

United States Patent 3,733,374 THIOPHOSPHATE ACETYL HYDRAZINES JamesZielinski, Kenilworth, N.J., assignor to Esso Research and EngineeringCompany No Drawing. Filed Apr. 24, 1970, Ser. No. 31,762 Int. Cl. C071?9/16; A0111 9/36 US. Cl. 260-923 12 Claims ABSTRACT OF THE DISCLOSUREOrganophosphorus compounds represented by the following structure:

P S-C R, \I'sL t. R. wherein R and R may or may not be the same and areselected from the group consisting of C -C alkoxy or alkyl; C Calkoxyalkyl; phenoxy optionally substituted by halogen, nitro or C Calkyl; phenylthio optionally substituted by halogen, nitro or C -Calkyl; C -C alkylthio, branched and unbranched; phenyl optionallysubstituted by halogen, nitro or C -C alkyl; R R and R may or may not bethe same and are selected from the group consisting of hydrogen; C -Calkyl, unsubstituted, branched or unbranched or optionally substitutedby halogen, C C alkoxy, C -C alkylthio, C -C alkylthioalkyl, C -C alkoxyalkyl or mono and dialkylaminoalkyl; phenyl optionally substituted byhalogen, nitro or C -C alkyl; X is either 0 or S and n is an integerranging from 1-3; R and R may be the same or different and are selectedfrom the group consisting of {212. flaiitm M. \i./. \i.)

substituted or unsubstituted aryl and heteroaryl; wherein Z=CN, COORCON(-R N0 SO N(R COOH, trihaloalkyl,

CR2 ii wherein L=O, S, SO, S0 NH, NR

g g ILQRQ 0 s hi, i,

SO, S0 A=OR SR NHR N(R and a is an integer ranging from 1 to 6; with theproviso that when R is the same as R then R cannot be R except when R orR is aryl or heteroaryl.

Such compounds as disclosed in this invention have been found to havecontact and systemic insecticidal and miticidal properties.

This invention relates to a new group of thiophosphate derivatives ofacetyl hydrazides. In one aspect, this invention relates to novelcompounds which exhibit excellent contact and systemic insecticidal andmiticidal properties while being relatively safe towards mammals. Inanother aspect, this invention relates to the use of such compounds aspesticides.

Dialkylthio and dithiophosphoro and phosphono acetyl hydrazides are notnovel for they have been described in a Belgian Pat. 713,363, which waspublished in October 3,733,374 Patented May 15,, 1973 in which R is alower alkyl radical; R is a lower alkyl radical or a lower alkoxyradical; the radicals represented by X are independently selected fromthe group consisting of oxygen and sulfur; R and R are independentlyselected from the group consisting of hydrogen, the methyl, ethyl,formyl, and acetyl radicals, and in combination can be selected from thegroup consisting of the ethylidene and methylidene radicals. The loweralkyl radicals suitable for R and R are aliphatic straight chain andbranched chain radicals having from 1 to 8 carbon atoms and include, forexample, the methyl, ethyl, n-propyl, isopropyl, amyl, octyl, andanalogous radicals. In the same way, the lower alkoxy radicals suitablefor R are straight chain and branched chain radicals having from 1 to 8carbon atoms and including the methoxy, ethoxy, n-propoxy, isopropoxy,amoxy, octoxy, and analogous radicals.

Some of these compounds, however, have been found to have a highmammalian toxicity level that restricts their use as selectivepesticides.

Therefore, the object of this invention is to provide suchhydrazine-containing thiophosphates that retain their activity asinsecticides and miticides but which are rendered much less toxic towardwarm-blooded animals.

Novel pesticides of this invention correspond to the followingstructural formula:

R X B3 X R l sltltm wherein R and R may or may not be the same and areselected from the group consisting of C -C alkoxy or alkyl, C -Calkoxyalkyl, phenoxy optionally substituted by halogen, nitro or C -Calkyl; phenylthio optionally substituted by halogen, nitro or C to Calkyl; C -C alkylthio, branched and unbranched; phenyl optionallysubstituted by halogen, nitro or C C alkyl; R R and R may or may not bethe same and are selected from the group consisting of hydrogen; C -Calkyl, unsubstituted, branched or unbranched or optionally substitutedby halogen, C -C alkoxy, C -C alkylthio, C -C alkylthioalkyl, C Calkoxyalkyl or mono and dialkylaminoalkyl; phenyl optionally substitutedby halogen, nitro or C -C alkyl; X is either 0 or S and n is an integerranging from 1-3; R and R may be the same or different and are selectedfrom the group consisting of i m iltlilfi. ,H,

at \t./. \t/

substituted and unsubstituted aryl and heteroaryl; wherein Z=CN, COORCON(-R N0 SO N(R COOH, trihalomethyl,

TABLE-Continued Compound No. Name Structures 160,0'-diethylphosphorothio-S- CH acetyl-2-methy1-2- (3cyano-2- H IIprQpyDhydraZide. (CzHaO) P S C HQCNHN C H C H2 C N0,0-dimethylphosphorothio-S- CH aeety1-2-methyl-Z-eyanomethyl II IIhydrazide. (CHaO) 2P S CH2CNHN C H2 C N 0,0-dimethylphosphorothio-S- CHacetyl-2-methyl-2-(3-cyano-2- II II propyl) hydrazide. (C1130) 2P S CHzCN EN 0 H- C H2 C N 19.. O ,0'-diethylphosphorothio-S- C H(2-ethylthioacetyl) -2-methy1-2- H il (Z-cyanoethyDhydrazide. (C2H50)1]? S CHCNHN S C 11 CH2CH2CN 0 ,0'-dimethylphosphorothio-S- C Haeetyl-2-methyl-2Qethoxy- II II ethyDhydrazide. (C11 0) 2P S CHzCNHN CH2 C H2 0 C 2H 21...- 0,0'-dimethylphosphorothlo-S- O 0 CHacetyl-2-methyl-2-carbomethoxy H g hydrazide. (C1130) P S CH N HN fi O CH3 0 0,0-dimethylphosphorothio-S- 0 CH acetyl-Z-methyl-Z-(N-phenyl- IIE]: carboxamido)hydrazide. (C11 0) 2P S OH; NHN

(I? NH O 23...'.:'.'.".; .1; O ,O'dimethylphosphorothio-s- 0 Hacety1-2-methyl-2-(N-methy II II earboxamido)hydrazide. (0 H O) 3P SCHzCNHN 1 NH C H3 0 24 0,0-dimethy1phosphorothio-S- 0 CHacetyl-2-methyl-2-(earbothio- II II ethoxy) hydrazide. (CH3 0) 2P S CHzCNHN C S C H H O 25.....'.. 0,0-dimethy1phosphorothio-S- 0 0 CHaeetyl-2-methyl-2-earboiso- H II propoxy hydrazide. (CH O)2P S CH2 NHNOiPr 26.. 0ethyl-ethylphosphonodithio-S- C 11 0 O 0 CHacetyl-1,2-dimethyl-2-(Z-cyano- II {J ethyDhydrazide. P S CH2 NN C2115H3 CHZCHZCN There are various ways for making one or more of theprecursors required in forming the compounds of the subject invention.

STEP I Process A.--Methyl hydrazine is reacted With an unsaturatedcyanide compound according to the following schematic equation:

NHzNH CH: CCN NHzNCHaCHsCN CH3 CH3 CH3 CH3 This type of reaction can becarried out at a temperature ranging from 20 to 80 0., preferably from 0to 40 C., and a reaction time ranging from 1 to 48 hours, preferablyfrom 4 to 12 hrs, with a mole ratio of A:B ranging from 2:1 to 5:1,preferably from 2:1 to 3: 1. The solvents for this invention can be anyones selected from the group consisting of ether, methyl cyanide,chloroform, water and benzene. Preferably, the solvent is water.

Process B.--Another alternate method for forming these precursors is toreact the methyl hydrazine with a chlorosubstituted pyridine compoundaccording to the following schematic equation:

0 O CHaNNHz-HCI o1 o1- NHzN -o1 H NHEIIIH @smoomon NI-IzIgCHzCN @--so3 nThis type of reaction can be carried out at a temperature ranging from20 to 100 C., preferably from 60 to 85, and a reaction time ranging from10 to 96 hours, preferably from 12 to 24 hrs. The solvents for thisreaction can be any alcohol such as for example, methanol, ethanol, orisopropanol. The mole ratios of A:B can range from 2:1 to 5:1,preferably from 2:1 to 3:1.

Process D.A still further method for forming one of the precursors is toreact the methyl hydrazine with 2- chloroethyl-ethyl ether according tothe following schematic equation:

NHQNH 01011 011 0 11 NH2NCH2CH2OC2H5 NHaNH-HCI This type of reaction canbe carried out at a temperature ranging from 20 to 200 C., preferablyfrom 60 to 85 C., the reaction time ranging from 8 to 96 hours,preferably from to 20 hrs., and the molar ratios of the reactants (A:B)ranging from 2:1 to 5:1, preferably from 2:1 to 3:1. The solvents can beany one selected from the group consisting of benzene, toluene andethanol.

Process B.A still further process for forming these precursors is toreact the methyl hydrazine with ethylchlorothioformate according to thefollowing schematic equation:

11 Base II NH IIIH ClCSCzHs i NHzBIIC S CzH5 Base-H01 CH3 CH3 This typeof reaction can be carried out at a temperature ranging from 59 to 100C. and preferably from 10 to 10 C. and a reaction time ranging from 2 to48 hours, preferably from 6 to hrs., and at molar ratios of thereactants (A:B) ranging from 1:1 to 4: 1, preferably from 1:1 to 2: l.The solvents for this reaction can be selected from the group consistingof methanol, ethanol, propanol, acetone and methylethyl ketone. Thisreaction is carried out in the presence of a base which can be oneselected from the group consisting of an alkali metal hydroxide, such assodium hydroxide and tertiary amines, such as triethylamine. The baseacts as an acid acceptor in this reaction.

Process F.Another method for forming these precursors for making thecompounds of this invention is to react the methyl hydrazine with methylisocyanate according to the following schematic equation:

0 ll NHzNH CHaNCO NH2NCNHCH3 This type of reaction can be carried out attemperatures ranging from to 50 C., preferably from 10 to 20 C., andreaction time ranging from 2 to 48 hours, preferably from 4 to 8 hrs.,at a molar ratio of reactants of A:B ranging from 1:1 to 4:1, preferablyfrom 1:1 to 2: l. The solvents for this reaction can be selected fromthe group consisting of ether, benzene and toluene.

8 STEP 11 Process A.-The second step in the process for making thecompounds of the subject invention is to react any one of the precursorsmade according to the above-described procedures with a chloroaceticanhydride according to the following schematic equation:

NHzN

CII2(|3HCN (A) 0 on:

ll CICHzCNHN CHZCHCN This type of reaction can be carried out attemperatures ranging from 0-150 C., preferably from to 90 C., and atreaction times ranging from 2 to 48 hours, preferably from 8 to 16 hrs.,and at molar ratios of A:B ranging from 1:1 to 4: 1, preferably from 1:1to 2:1. The solvents for this reaction can be selected from the groupconsisting of ether, benzene and toluene.

Process B.An alternative method for carrying out this Step II of thesubject process can be to react any one of the precursors made accordingto the first step with a chloroacetyl chloride compound according to thefollowing schematic equation:

I] Base NIIzN ClCHzCCI CHzCHCN (B) CH5 (A) H ClCHzCNHN Base-H01 CHzCHCNThis type of reaction is carried out at a temperature ranging from 20 to50 C., preferably from l0 to 20 C., the reaction time ranging from 1 to48 hours, preferably from 3 to 8 hrs., and at molar ratios of A:Branging from 1:1 to 5:1, preferably from 1:1 to 2:1. The base for thisreaction can be one selected from the group consisting of sodiumhydroxide, triethylamine and other alkali metal hydroxides or tertiaryamines such as tripropylamine, and the like. This base material acts asan acid acceptor. The solvents for this reaction can be selected fromthe group consisting of ether, benzene and toluene.

Process C.A still further alternative method for carrying out Step II togive rise to branched analogs of the process is to react any one of theprecursors made according to Step I of the process with a bromopropionylbromide according to the following schematic equation:

CH3 K Base NH2 Br-CH Br CH2OH2CN H3 0 CH3 ll BrCI-I NHN Base-HBr aCHzCHzCN This type of reaction can be carried out at a temperatureranging from 30 to C., preferably from 10 to 20 C., and a reaction timeranging from 2 to 48 hours, preferably 4 to 10 hrs., and the reactantsare present in a molar ratio of A:B ranging from 1:1 to 5: 1, preferablyfrom 1:1 to 2:1.

This type of reaction is carried out in the presence of a base which canbe either an alkali metal hydroxide or a tertiary amine such astriethylamine. The solvents for this reaction are selected from thegroup consisting of ether, benzene and toluene.

Process D.-A still further alternative reaction for Step II to give riseto extended chain compounds is the reaction of any of the reactants ofStep I with acrylyl chloride according to the following schematicequation:

CH3 V II Base NHzN CH2=CHOCl CHzCHzCN 0 CH: 11 CHz=CH NHN Base-H01CH2CH2CN This type of reaction was carried out at a temperature rangingfrom -20 to 100 C., preferably from 10 to 20 C. at a reaction timeranging from 2 to 72 hours, preferably from 4 to 12 hrs., and a moleratio of the reactants of A:B, ranging from 1:1 to 5:1. The reaction iscarried out in the presence of a base, said base being either an alkalimetal hydroxide or a tertiary amine, such as tri ethylamine. Thesolvents are any one selected from the group consisting of ether,tetrahydrofuran, benzene and toluene.

STEP III Process A.--The final step in the preparation of thesecompounds can be schematically described as follows:

t M if a \P s M oN-N Wherein the reaction is carried out at atemperature ranging from 20 to 150 (3., preferably from 40 to 70, at areaction time ranging from 2 to 72 hours, preferably from 4 to 12 hrs.The salt derivative (M) of the phosphorus acid is potassium, sodium,triethyl ammonium, ammonium, etc., salt. The solvents for this reactioncan be selected from the group consisting of acetonitrile, benzene,acetone, tetrahydrofuran, toluene, dimethylformamide.

Process B.An alternative procedure for this step in the overallsynthesis can be described according to the following schematicequation:

CHzCHzCN O E) /OHa (onlihohl. S CHaCHzNHN CHzCHzCN This type of reactioncan be carried out at a temperature ranging from 10 to 100 0, preferablyfrom 10 to 40 C., at a reaction time ranging from 2 to 48 hours,preferably from 4 to 12 hrs., and a mole ratio of A:B ranging from 1:1to 4:1, preferably from 1:1 to 2: 1. The solvents for this reaction canbe selected from the group consisting of methanol, ethanol andisopropanol.

The compounds of the invention have general insecticidal properties.They are especially useful in certain types of insect control.

Insecticidal compositions of the invention are prepared by admixing oneor more of the active ingredients defined heretofore, in insecticidallyeffective amounts with a conditioning agent of the kind used andreferred to in the art as a pest control adjuvant or modifier to provideformu- 10 lations adapted for ready and eflicient application to soil orplants using conventional applicator equipment.

Thus, the insecticidal compositions or formulations are prepared in theform of solids or liquids. Solid compositions are preferably in the formof granulars or dusts.

The compositions can be compounded to give homogeneous free-flowingdusts by admixing the active compound or compounds with finely dividedsolids preferably talc, natural clays, pyrophyllite, diatomaceous earth,or flours such as walnut shell, wheat, redwood, soya bean, andcottonseed flours. Other inert solid conditioning agents or carriers ofthe kind conventionally employed in preparing pest control compositionsin powdered form can be used.

Granulars can be compounded by absorbing the compound in liquid formonto a preformed granular diluent. Such diluents as natural clays,pyrophyllite, diatomaceous earth, flours such as walnut shell, as wellas granular sand can be employed.

In addition, granulars can also be compounded by admixing the activeingredient with one of the powdered diluents described hereinabove,followed by the step of either pelleting or extruding the mixture.

Liquid compositions of the invention are prepared in the usual way byadmixing one or more of the active ingredient with a suitable liquiddiluent medium. In the cases where the compounds are liquids, they maybe sprayed in ultra low volume as such. With certain solvents, such asalkylated naphthalene or other aromatic petroleum solvents, dirnethylformamide, cycloketone, relatively high up to about 50% by weight ormore concentration of the active ingredient can be obtained in solution.

The insecticidal compositions of the invention whether in the form ofdusts or liquids, preferably also include a surface-active agentsometimes referred to in the art as a wetting, dispersing, oremulsifying agent. These agents, which will be referred to hereinaftermore simply as surface-active dispersing agents, cause the compositionsto be easily dispersed in water to give aqueous sprays which, for themost part, constitute a desirable composition for application.

The surface-active dispersing agents employed can be of the anionic,cationic, or nonionic type and include, for example, sodium andpotassium oleate, the amine salts of oleic acid, such as morpholine anddimethylamine oleates, the sulfonated animal and vegetable oils, such assulfonated fish and castor oils, sulfonated petroleum oils, sulfonatedacyclic hydrocarbons, sodium salt of lignin sulfonic acid (goulac),alkylnaphthalene sodium sulfonate, sodium salts of sulfonatedcondensation products of naphthalene and formaldehyde, sodium laurylsulfate, disodium monolauryl phosphate, sorbitol laurate,pentaerythritol monostearate, glycerol monostearate, diglycol oleate,polyethylene oxides, ethylene oxide condensation products with stearylalcohol and alkylphenol, polyvinyl alcohols, salts, such as the acetateof polyamines from reductive amination of ethylene/carbon monoxidepolymers, laurylamine hydrochloride, laurylpyridinium bromide, stearyltrimethylammonium bromide, cetyldimethylbenzyl ammonium chloride,lauryldimethylamine oxide, and the like. Generally, the surface-activeagent will not comprise more than about 5 to 15% by weight of thecomposition, and in certain compositions the percentage will be 1% orless. Usually, the minimum lower concentration will be 0.1%.

The insecticidal compositions are applied either as a spray, granular ora dust to the locus or area to be protected from undesirable insects.Such application can be made directly upon the locus or area and theplants thereon during the period of insect infestation in order todestroy the insects, but preferably, the application is made in advanceof an anticipated insect infestation to prevent such infestation. Thus,the compositions can be applied as aqueous foliar sprays but can also beapplied as sprays directly to the surface of the soil. Alternatively,the dry powdered compositions can be dusted directly on the plants or onthe soil.

The active compound is, of course, applied in an amount sufficient toexert the desired insecticidal action. The amount of the active compoundpresent in the compositions as actually applied for insect control willvary with the manner of application, the particular insects for whichcontrol is sought, the purpose for which the application is being made,and like variables. In general, the 1H- secticidal compositions asapplied in the form of a spray, dust or granular, will contain fromabout 0.1% to 100% by weight of the active compound.

Fertilizer materials, other insecticidal agents, and other pest controlagents such as insecticides and fungicides can be included in theinsecticidal compositions of the invention if desired.

The term carrier" or diluent as used herein means a material, which canbe inorganic or organic and synthetic or of natural origin, with whichthe active ingredient is mixed or formulated to facilitate its storage,transport, and handling and application to the plants to be protected.The carrier is preferably biologically and chemically inert and, asused, can be a solid or fluid. When solid carriers are used, they arepreferably particulate, granular, or pelleted; however, other shapes andsizes of solid carrier can be employed as well. Such preferable solidcarriers can be natural occurring minerals-although subsequentlysubjected to grinding, sieving, purification, and/or othertreatments-including, for example, gypsum; tripolite; diatomaceousearth; mineral silicates such as mica, vermiculite, talc, andpyrophyllite; clays of the montmorillonite, kaolinite, or attapulgitegroups; calcium or magnesium limes, or calcite and dolomite; etc.Carriers produced synthetically, as for example, synthetic hydratedsilica oxides and synthetic calcium silicates can also be used, and manyproprietary products of this type are available commercially. Thecarrier can also be an elemental substance such as sulfur or carbon,preferably an activated carbon. If the carrier possesses intrinsiccatalytic activity such that it would decompose the active ingredient,it is advantageous to incorporate a stabilizing agent, as for example,polyglycols such as diethylene glycol, to neutralize this activity andthereby prevent possible decomposition of the derivatives.

For some purposes, a resinous or waxy carrier can be used, preferablyone which is solvent soluble or thermoplastic, including fusible.Examples of such carriers are natural or synthetic resins such as acoumarone resin, rosin, copal, shellac, dammar, polyvinyl chloride,styrene polymers and copolymers, a solid grade of polychlorophenol suchas is available under the registered trademark Aroclor, a bitumen, anasphaltite, a wax for example, beeswax or a mineral wax such as paraffinwax or montan wax, or a chlorinated mineral wax, or a microcrystallinewax such as those available under the registered trademark Mikrovan Wax.Compositions comprising such resinous or waxy carriers are preferably ingranular or pelleted form.

Fluid carriers can be liquids, as for example, water, or an organicfluid, including a liquefied normally vaporous or gaseous material, or avaporous or gaseous material, and can be solvents or nonsolvents for theactive material. For example, the horticultural petroleum spray oilsboiling in the range of from about 275 to about 575 F., or boiling inthe range of about 575 to about 1,000 F. and having an unsulfonatableresidue of at least about 75% and preferably of at least about 90%, ormixtures of these two types of oil, are particularly suitable liquidcarriers.

The carrier can be mixed or formulated with the active material duringits manufacture or at any stage subsequently. The carrier can be mixedor formulated with the active material in any proportion depending onthe 12 nature of the carrier. One or more carriers, moreover, can beused in combination.

The compositions of this invention can be concentrates, suitable forstorage or transport and containing, for example, from about 5 to about90% by weight of the active ingredient, preferably from about 20 toabout wt. percent. These concentrates can be diluted with the same ordifferent carrier to a concentration suitable for application. Thecompositions of this invention may also be dilute compositions suitablefor application. In general, concentrations of about 0.1 to about 10% byweight, of active material based on the total weight of the compositionare satisfactory, although lower and higher concentrations can beapplied if necessary.

The compositions of this invention can also be formulated as dusts.These comprise an intimate admixture of the active ingredient and afinely powdered solid carrier such as aforedescribed. The powderedcarriers can be oil-treated to improve adhesion to the surface to whichthey are applied. These dusts can be concentrates, in which case ahighly sorptive carrier is preferably used. These require dilution withthe same or a different finely powdered carrier, which can be of lowersorptive capacity, to a concentration suitable for application.

The compositions of the invention can be formulated as wettable powderscomprising a major proportion of the active ingredient mixed with adispersing, i.e., deflocculating or suspending agent, and if desired, afinely divided solid carrier and/or a wetting agent. The activeingredient can be in particulate form or adsorbed on the carrier andpreferably constitutes at least about 10%, more preferably at leastabout 25%, by weight of the composition. The concentration of thedispersing agent should in general be between about 0.5 and about 5% byweight of the total composition, although larger or smaller amounts canbe used if desired.

The dispersing agent used in the composition of this invention can beany substance having definite dispersing, i.e., deflocculating orsuspending, properties as distinct from wetting properties, althoughthese substances can also possess wetting properties as well.

The dispersant or dispersing agent used can be protective colloids suchas gelatin, glue, casein, gums, or a synthetic polymeric material suchas polyvinyl alcohol and methyl cellulose. Preferably, however, thedispersants or dispersing agents used are sodium or calcium salts ofhigh molecular weight sulfonic acids, as for example, the sodium orcalcium salts of lignin sulfonic acids derived from sulfite cellulosewaste liquors. The calcium or sodium salts of condensed aryl sulfonicacid, for example, the products known as Tamol 731, are also suitable.

The wetting agents used can be nonionic type surfactants, as forexample, the condensation products of fatty acids containing at least12, preferably 16 to 20, carbon atoms in the molecule, or abietic acidor naphthenic acid obtained in the refining of petroleum lubricating oilfractions with alkylene oxides such as ethylene oxide or propyleneoxide, or with both ethylene oxide and propylene oxide, as for example,the condensation product of oleic acid and ethylene oxide containingabout 6 to 15 ethylene oxide units in the molecule. Other nonionicwetting agents like polyalkylene oxide polymers, commercially known asPluronics can be used. Partial esters of the above acids with polyhydricalcohols such as glycerol, polyglycerol, sorbitol, or mannitol can alsobe used.

Suitable anionic wetting agents include the alkali metal salts,preferably sodium salts, of sulfuric acid esters or sulfonic acidscontaining at least 10 carbon atoms in a molecule, for example, thesodium secondary alkyl sulfates, dialkyl sodium sulfosuccinate availableunder the registered trademark Teepol, sodium salts of sulfonated castoroil, sodium dodecyl benzene sulfonate.

Granulated or pelleted compositions comprising a suitable carrier havingthe active ingredient incorporated therein are also included in thisinvention. These can be 13 prepared by impregnating a granular carrierwith a solution of the inert ingredient or by granulating a mixture ofa. finely divided solid carrier and the active ingredient. The carrierused can consist of or contain a fertilizer or fertilizer mixture, asfor example, a superphosphate.

The compositions of this invention can also be formulated as solutionsof the active ingredient in an organic solvent or mixture of solvents,such as for example, alcohols; ketones, especially acetone; ethers;hydrocarbons; etc.

Where the toxicant itself is a liquid these materials can be sprayed oncrops or insects without further dilution.

Petroleum hydrocarbon fractions used as solvents should preferably havea flash point above 73 F., an example of this being a refined aromaticextract of kerosene. Auxiliary solvents such as alcohols, ketones, andpolyalkylene glycol ethers and esters can be used in conjunction withthese petroleum solvents.

Compositions of the present invention can also be formulated asemulsifiable concentrates which are concentrated solutions or dispersionof the active ingredient in an organic liquid, preferably awater-insoluble organic liquid, containing an added emulsifying agent.These concentrates can also contain a proportion of water, for example,up to about 50% by volume, based on the total composition, to facilitatesubsequent dilution with water. Suitable organic liquids include, e.g.,the above petroleum hydrocarbon fractions previously described.

The emulsifying agent can be of the type producing water-in-oil typeemulsions which are suitable for application by low volume spraying, oran emulsifier of the type producing oil-in-water emulsions can be used,producing concentrates which can be diluted with relatively largevolumes of water for application by high volume spraying or relativelysmall volumes of Water for low volume spraying. In such emulsions, theactive ingredient is preferably in a nonaqueous phase.

The present invention is further illustrated in greater detail by thefollowing examples, but it is to be understood that the presentinvention in its broadest aspects, is not necessarily limited in termsof the reactants, or specific temperatures, residence times, separationtechniques and other process conditions, etc.; or dosage level, exposuretimes, test species used, etc. by which the compounds and/orcompositions described and claimed are prepared and/ or used.

EXAMPLE 1 Preparation of l-methyl-1a(6-chloro-2-pyridyl) hydrazine (StepI, Process B) Methylhydrazine (138.3 g., 3.0 moles) was added rapidlymin.) to a solution of 2,6-dichloropyridine (148 g., 1.0 mol) in a 1:1ethanol-methanol (400 ml.), allowed to stir overnight and refluxed for 6hours. The solvents were removed in vacuo to give an oil with 2 layers.The lower layer 'was distilled to yield a clear oil, B.P. 83-92 C., at0.02-0.05 mm. Hg; 100 gms. (64%).

Analysis.-Calcd. for C H ClN (percent): C, 45.7; H, 5.1; N, 26.7; C1.22.5. Found (percent): C, 45.9; H, 5.2; N, 26.1; C1, 22.2.

Preparation of l-methyl-l(6-chloro-2-pyridyl)-2-chloroacetyl hydrazide(Step II, Process B) To a cooled solution ofl-methyl-l-(6-chloro-2-pyridyl) hydrazine (22.0 g., 0.14 mol) andtriethylamine (14.2 g., 0.14 mol) in 100 ml. ether was added dropwisechloroacetyl chloride (15.9 g., 0.14 mol) over a 2 hour period. Themixture was allowed to stir at room temperature for 48 hours, filteredand washed with H O. Removal of the ether in vacuo gave 25.2 g. (77%) ofthe hydrazide, a small sample of which was recrystallized from EtOAc,M.P. 107-110".

14 Analysis.Calcd. for C H Cl N O (percent): C, 41.0; H, 3.9; N, 17.9;Cl, 30.3. Found (percent): C, 4 .6; H,

4.7; N, 17.4; CI, 29.4.

Preparation of 0,0'-diethylphosphorothio-S-acetyl 2-methyl-Z-(6-chloro-2-pyridyl)hydrazide (Compound 2) (Step III, ProcessA) l-methyl-l(6-chloro-2-pyridyl)-2 chloroacetyl hydrazide (14 g., 0.06mol) and diethylphosphorothioic acid ammonium salt (11.6 g., 0.062 mol)were combined in 300 ml. CH CN and refluxed for 2 hours. The reactionwas filtered and evaporated in vacuo to yield a clear yellow oil whichwas distilled in vacuo to yield a dark 'viscous oil, 15.6 gm. (78%).Recrystallization from ether-pentane gave 14.7 g. (7 3 of 0,0diethylphosphoro-thio-S-acetyl- 2-methyl-2(6-chloro-2-pyridyl)hydrazide, MP. 61.5- 63 C. The structure was confirmed by NMR.

Analysis.Calcd. for C H ClN O PS (percent): C, 39.2; H, 5.2; N, 11.4;C1, 9.7; P, 8.4; S, 8.7. Found (percent): C, 39.6; H, 5.4; N, 11.5; CI,9.8; P, 8.3; S, 8.9.

EXAMPLE 2 r Preparation of 1-methyl-1(2 cyanopropyl) hydrazine (Compound15) (Step I, Process A) A solution of 67 g. (1 mole) methacrylonitrilein 100 ml. methanol was added dropwise, rapidly, at room temperature toa solution of 46 g. (1 mol) methylhydrazine in 300 ml. methanol. Afterstirring overnight, there was no evidence of reaction and 200 ml. H Owas added in two portions. The temperature rose to 31. The solutionstirred for 48 hrs. and was evaporated in vacuo with ethanol being addedto azeotrope the H 0. The oil was vacuum distilled to give 59.3 g. (52%)of A: 53-57 at 0.05 mm. IR and NMR verified structure.

Analysis.Calcd. for C H N (percent): C, 53.1; H, 9.7; N, 37.2. Found(percent): C, 52.2; H, 9.4; N, 36.3.

Preparation of 1 methyl-1-=(2-cyanopropyl)-2-(2-chloroacetyl) hydrazide(Compound 15 (Step II, Process A) A solution of 29.1 g. (0.17 mol)chloroacetic anhydride in 250 ml. benzene was added dropwise to asolution of A (19.3 g., 0.17 mol) in 50 ml. benzene. The temperaturerose to 30 and the solution stirred overnight at room temperature. Tothis solution was added 100 ml. 5% NaHCO solution. The layers wereseparated and the benzene layer washed with H O. The combined H O layerswere extracted with CHCI and the CHCl layers dried (MgSO and evaporatedin vacuo to give 20.7 g. (63%) B as a heavy oil. NMR and IR verified thestructure. A small sample was recrystallized from ether-ethanol, M.P.53-56.5.

Analysis.Calcd. for C H ClN O (percent): C, 44.3; E 63; N, 22.1. Found(percent): C, 44.5; H, 6.2; N, 21.9.

Preparation of 1(dimethylphosphorothioacetyl)-methyl- 2(2-cyanopropyl)hydrazide (Compound 15 (Step III, Process A) l-methyl-1(2-cyanopropyl)-2chloroacetyl hydrazide (15.2 g., 0.08 mol) and dimethyl phosphorothioicacid ammonium salt (12.9 g., 0.081 mol) were combined in 200 ml. OH CNand heated at reflux (82) for 5 hrs'., cooled and allowed to stir atroom temperature overnight. The 'CH CN solution was decanted from thegummy solid and evaporated in vacuo to give a clear, colorless oil Whichwas partitioned between H 0 and ether. After ether extraction, the H 0layer was further extracted with benzene and the organic layersdiscarded (these washings remove (CH O) P(O)SCI-I The water layer waseX- tracted with CHCl and EtOAc. The organic layers were dried (MgSO andevaporated in vacuo to yield 14.2 g. (60%) of Compound 15 as a clearamber oil. The structure was confirmed by NMR (purity about 85%).

15 EXAMPLE 3 Preparation of 1-methyl-1(2-cyanoethyl) hydrazine (Compound11) (Step I, Process A) A solution of methyl hydrazine (46.1 g., 1 mol)in 200 ml. ether was added dropwise to a solution of acrylonitrile (53.1g., 1 mol) in 200 ml. ether. The addition is controlled to keep thetemperature between and C. and is then allowed to stir overnight at roomtemperature. The ether was removed in vacuo to give a clear, colorlessoil which was distilled to give the desired product, B.P. 55 65 C. at0.08-0.4 mm. Hg. The structure was verified by IR and NMR.

Preparation of l-methyl-l(2-cyanoethyl)-2-acrylyl hydrazide (Compound11) (Step II, Process D) A solution of acrylyl chloride (45.3 g., 0.5mol) in 100 ml. tetrahydrofuran was added to a cooled (10 C.) solutionof 1-methyl-1(2-cyanoethyl) hydrazine and triethylamine (51 g., 0.51mol) in 200 ml. tetrahydrofuran. The reaction was stirred at roomtemperature overnight, filtered and evaporated in vacuo to give a yellowoil which was dissolved in CHCl and washed with water, dried (MgSOevaporated in vacuo. Cooling gave a yellow solid which wasrecrystallized from ether-ethyl acetate, M.P. 63.5-66". The structurewas confirmed by NMR.

Analysis.-Calcd. for C H N O (percent): C, 54.8; H, 7.2; N, 27.4. Found(percent): C, 54.5; H, 7.5; N, 27.2.

Preparation of 1[0,0 diethylphosphorothio-S(3-propionyl)]-2-methyl-2(2-cyanoethyl) hydrazide (Compound 11) (Step III, Process B)Diethylmonothiophosphoric acid (25.5 g., 0.15 mol) was added in oneportion to a suspension of l-methyl- 1(2-cyanoethyl)-2-acrylyl hydrazide(23 g., 0.15 mol) in 200 ml. benzene. The resulting solution was allowedto stir overnight, was warmed to 50 C. for 3 hrs. and allowed to stir atroom temperature for 48 hrs. The benzene solution was washed with 5%NaHCO water, dried (MgSO evaporated in vacuo to give a viscous oil,whose NMR was consistent with the desired structure.

EXAMPLE 4 Preparation of 1 methyl 1(2-cyanoethyl)-2(2-chloroacetyl)hydrazide (Compound 19) (Step II, Process A solution of chloroacetylchloride (33.9 g., 0.3 mol) in 50 ml. ether was added dropwise to acooled (5 to 10 C.) solution of 1-methyl-1(2-cyanoethyl) hydrazine (29.7g., 0.3 mol-see Example 3, Step I for preparation) and triethylamine (31g., 0.3 mol) in 200 ml. ether over a period of 1.5 hrs. The mixture wasstirred overnight at room temperature, filtered and the solid washedwith water. The water washings were back extracted with ethyl acetate,dried (MgSO and evaporated in vacuo. These solids were combined with theoriginal water washed material to give 30 gins. (60%) of the hydrazide,m.p. 9095.

Analysis.Calcd. for C H ClN O (percent): C, 41.0; H, 5.7; N, 23.8; CI,20.2. Found (percent): C, 41.5; H, 5.8; N, 22.6; C1, 20.7.

Preparation of l-methyl-l (2-cyanoethyl)-2(2-ethylthioacetyl) hydrazide(Compound 19) Ethyl mercaptan (31.0 g., 0.5 mol) was added in oneportion to a solution of sodium ethoxide in ethanol [prepared by theaddition of sodium (11.5 g., 0.5 g.- atoms) to 300 ml. absoluteethanol]. 1-methyl-1(2- cyanoethyl) 2(2 chloroacetyl) hydrazide (87.8g., 0.5 mol) was added in one portion to this solution and 250 ml. ofethanol were also added. The mixture was stirred for 24 hrs, filteredand the solvent removed in vacuo.

The remaining oil was partitioned between CHCl and water. The CHCl layerwas dried (MgSO filtered and evaporated in vacuo to yield a tan solidwhich was recrystallized from ether-ethanol, M.P. 51-53.

Analysis.Calcd. for C H N OS (percent): C, 47.7; H, 6.9; N, 20.9; S,15.9. Found (percent): C, 47.9; H, 7.6; N, 20.8; S, 16.8.

Preparation of 0,0-diethylphosphorothio-S(2-ethylthioacetyl)-Z-methyl2(2 cyanoethyl) hydrazide (Compound 19) (Step III, Process A) A solutionof sulfuryl chloride (9.45 g., 0.07 mol) was added dropwise to asolution of 1 methyl 1(2 cyanoethyl)-2(2-ethylthioacetyl) hydrazide(14.1 g., 0.07 mol) in 70 ml. CHCl The solvent was removed in vacuo andthe tan oily slurry is dissolved in 150 ml. CH CN to which was addeddiethylphosphorothioic acid ammonium salt (13.1 g., 0.07 mol) and heatedat 81 C. for 3.5 hrs. The solvent was removed in vacuo and the resultingbrown oil partitioned between H 0 and ether. The ether layer wasdiscarded and the H 0 layer further extracted with CHCl which was dried(MgSO filtered and evaporated in vacuo to yield a dark brown oil. ThinLayer Chromatographic analysis on silica gel showed the presence of onemajor spot (Compound 19) with R =0.l9 (ethyl acetate). The structure wasconfirmed by NMR.

EXAMPLE 5 Preparation of l-methyl-l-carbomethoxy hydrazine (Compound 21)(Step I, Process E) Methyl chloroformate (189 g., 2 mols) was addeddropwise to a cooled (0 C.) solution sodium hydroxide (82.5 g., 2 mols)and methyl hydrazine (92 g., 2 mols) in 500 ml. ethanol. The mixture wasstirred at room temperature for 1 hr., filtered and the solvent removedin vacuo to give a colorless oil which was distilled, B.P. 3747 C. at0.1 mm. Hg. NMR and IR confirmed the structure.

Preparation of 1 methyl 1 carbomethoxy-2(2-chloroacetyl) hydrazide(Compound 21) (Step II, Process In 3 portions, a solution ofchloroacetic anhydride (102.6 g., 0.6 mol) in 600 ml. benzene was addedto a solution of l-methyl-l-carbomethoxy hydrazine (62.4 g., 0.6 mol) inml. benzene. The solution stirred at room temperature overnight, wasneutralized with a saturated solution of sodium bicarbonate. The benzenelayer was dried (MgSO filtered and evaporated in vacuo to give a smallamount of material. The water layer was submitted to liquid-liquidextraction with ethyl acetate. The EtOAc was dried (MgSO filtered andevaporated to give a heavy oil. NMR and IR confirmed the structure.

Preparation of 0,0 dimethylphosphorothio S-acetyl-Z- methyl 2carbomethoxy hydrazide (Compound 21) (Step III, Process A) l-methyl-lcarbomethoxy 2 chloroacetyl hydrazide (18.1 g., 0.1 mol) anddimethylphosphorothioic acid ammonium salt (15.9 g., 0.1 mol) werecombined in 100 ml. CH CN and heated to 60 C. for 3 hrs. and allowed tostir overnight at room temperature. The reaction was filtered andevaporated in vacuo to give an oil which was suspended in H 0 andextracted with CHCl The CHCl extracts were combined, dried (MgSOfiltered and evaporated in vacuo. The remaining oil was kept under highvacuum overnight. The structure was confirmed by NMR. Thin LayerChromatographic analysis on silica gel showed the presence of one majorspot (Compound 21) with R =0.19 (ethyl acetate).

17 EXAMPLE 6 Preparation of 2-methyl-4-phenyl semicarbazide (Compound22) (Step 1, Process F) A solution of phenyl isocyanate (119 g., 1.0mol) in 100 ml. ether was added dropwise to a cooled (30 C.) solution ofmethyl hydrazine (46 g., 1.0 mol) in 200 ml. ether. The mixture stirredovernight and the solid which formed was filtered and recrystallizedfrom ethanol to give the product, M.P. 91-93" C.

Analysis.-Calcd. for C H N O (percent): C, 58.5; H, 6.1; N, 25.6. Found(percent): C, 58.0; H, 6.9; N, 25.3.

Preparation of 1(2 chloroacetyl) 2 methyl-4-phenyl semicarbazide(Compound 22) (Step II, Process A) A solution of chloroacetic anhydride(34.2 g., 0.2 mol) in 150 ml. benzene was added in one portion to asolution of 2-methyl-4-phenyl semicarbazide (33.0 g., 0.2 mol) in 100ml. benzene and allowed to stir at room temperature overnight. 100 ml.of a saturated solution of sodium bicarbonate was added and the solidwhich resulted removed by filtration and were recrystallized from ethylacetate, M.P. 131133.

Analysis.Calcd. for C H ClN O (percent): C, 49.7; H, 4.9; N, 17.4; C1,14.7. Found (percent): C, 48.8; H, 5.4; N, 16.7; C1, 15.0.

Preparation of 1(0,0-dimethylphosphorothio-S-acetyl)- 2phenyl-2(N-phenylearboxamido) hydrazide (compound 22) (Step III, ProcessA) 1 chloroacetyl-2-rnethyl-4-phenyl semicarbazide (19.3 g., 0.08 mol)and dimethylphosphorothioic acid ammonium salt (13.0 g., 0.08 mol) werecombined in 150 ml. acetonitrile and heated to 65 C. for 1.5 hrs.,stirred overnight at room temperature, and heated to 65 for anadditional 1.5 hrs. The reaction mixture was evaporated in vacuo and thewhite oil partitioned between 50 ml. water and 50 ml. ether. Threelayers resulted. The ether layer was discarded. Chloroform (100 ml.) wasadded to the H O-oil mixture. The chloroform layer was collected and theH layer further washed with chloroform. The combined chloroform layerswere dried (MgSO filtered, evaporated in vacuo and subjected to highvacuum overnight. A clear, colorless gum resulted which was crystallizedfrom ethanol, M.P. 112-115 The structure was confirmed by NMR.

Analysis.Calcd. for C H N O PS (percent): C, 41.5; H, 5.2; N, 12.1; P,8.9. Found (percent): C, 41.6; H, 5.4; N, 12.3; P, 8.9.

The following compounds were made according to the same proceduredescribed hereinabove with the preceding examples:

EXAMPLE 7 Preparation of 0,0-diethylphosphorodithio-S-acetyl-Z-methyl-2-(2-cyanoethyl) hydrazide (Compound 1)l-methyl-l(2-cyanoethyl)-2-chloroacety1 hydrazide was reacted withdiethyl phosphorodithioic acid ammonium salt to give a viscous oil whichwas identified as0,0-diethylphosphorodithio-S-acetyl-2-methyl-2-(2-cyanoethyl) hydrazide.This structure was confirmed by NMR. The TLC* was (EtOAc) Rg=0.54.

EXAMPLE 8 Preparation of 0,0-diethylphosphorothio-S-acetyl-2-methyl-Z-phenyl hydrazide (Compound 3) l-methyl-l-phenyl-2-chloroacetylhydrazide was reacted with diethylphosphorothioic acid ammonium salt togive lLC.Thln Layer Chromatography (run on silica gel precoated slide).

18 a black oil which was identified as0,0-diethy1phosphorothio-S-acetyl-Z-methyl-2-phenyl hydrazide. Thisstructure was confirmed by NMR.

EXAMPLE 9 Preparation of 0,0-dimethylphosphorothio-S-acetyl-2-methyl-2(2-cyanoethyl)hydrazide (Compound 4) 1-methyl-l(Z-cyanoethyl)-2-chloroacetyl hydrazide was reacted withdimethylphosphorothioic acid ammonium salt to give an amber oil whichwas identified as 0,0- dimethylphosphorothio-S-acetyl2-methyl-2-(2-cyanoethyl)hydrazide. This structure was confirmed by NMR.

EXAMPLE 10 Preparation of 0,0'-dimethylphosphorodithio-S-acetyl-2-methyl-Z-(Lcyanoethyl) hydrazide (Compound 5) vl-methyl-l(Z-cyanoethyl)-2-chloroacetyl hydrazide was reacted withdimethylphosphorodithioic acid ammonium salt to give an amber oil whichwas identified as 0,0-dimethylphosphorodithio-S-acetyl2-methyl-2-(2-cyanoethyl) hydrazide. This structure was confirmed byNMR.

EXAMPLE 11 Preparation of 0,0'-diethylphosphorothio-S-acetyl-Z-methyl-2(2-cyanopropyl) hydrazide (Compound 6) 1methyl-1(2-cyanopropyl)-2-chloroacetyl hydrazide was reacted withdiethylphosphorothioic acid ammonium saltto give an amber oil which wasidentified as 0,0- diethylphosphorothio Sacetyl-2-methyl-2-(2-cyanopropyl) hydrazide. This structure wasconfirmed by NMR. The TLC was (10% EtOH/EtOAc) R =0.15.

EXAMPLE 12 Preparation of 0,0-diethylphosphorothio-S-acetyl-Z-methyl-2-(2-carboethoxyethyl) hydrazide (Compound 7) 1 methyl-l(2-carboethoxyethyl)-2-chloroacetyl hydrazide was reacted withdiethylphosphorothioic acid ammonium salt to give a clear yellow oilwhich was identified as O,'O'diethylphosphorothio-S-acetyl-Z-methyl-2-(2-carboethoxyethyl) hydrazide.This structure was confirmed by NMR. The TLC was (EtOAc) R =0.24.

EXAMPLE 13 Preparation of 0,0 diethylphosphorothio S acetyl-2-methyl-2[2(N,N dimethylcarboxamido) ethyHhydrazide (Compound 8) EXAMPLE14 Preparation of O,O-diethylphosphorothio-S-acetyl-Z-methyl-2'(2-methylthioethyl)hydrazide (Compound 9) 1methyl-1(Z-methylthioethyl)-2-chloroacetyl hydrazide was reacted withdiethylphosphorothioic acid ammonium salt to give a tan oil which wasidentified as 0,0- diethylphosphorothio-S-acetyl2-methyl-2-(Z-methylthioethyl)hydrazide. This structure was confirmed byNMR. The TLC was (EtOAc) R;=0.23.

EXAMPLE 15 Preparation of 0,0-diethylphosphorothio-S-acetyl-2-methyl-2-(2-ethoxyethyl) hydrazide (Compound 10) l-methyl-l(2-ethoxyethyl)-2-chloroacetyl hydrazide was reacted withdiethylphosphorothioic acid ammonium salt to give an orange oil whichwas identified as 0,0-dieth- 19 ylphosphorothio-S-acetyl2-methyl-2-(Z-ethoxyethyl) hydrazide. This structure was confirmed byNMR. TLC was (EtOAc) R;=0.23.

EXAMPLE 16 Preparation of O-ethyl S n propylphosphorodithio-S- acetyl 2methyl-2(2-cyanoethyl) hydrazide (Compound 12) l-methyl-l(Z-cyanoethyl)-2-chloroacetyl hydrazide was reacted with Oethyl-S-n-propyl phosphorodithioic acid potassium salt to give an amberoil which was identified asO-ethyl-S-n-propylphosphorodithio-S-acetyl-2-methyl-2(2-cyanoethyl)hydrazide. This structure was confirmed by NMR. The TLCwas (EtOAc) R =0.24.

EXAMPLE 17 Preparation of 0,0'-diethylphosphorothio-S(2-propionyl)-2-methyl-2(2-cyanoethyl) hydrazide (Compound 11) 1methyl-1(2-cyanoethyl)-2-acrylyl hydrazide was reacted withdiethylphosphorothioic acid to give an amber oil which was identified as0,0'-diethylphosphorothio-S (2 propionyl)-2-methyl-2(Z-cyanoethyl)hydrazide. This structure was confirmed by NMR.

EXAMPLE 18 Preparation of 0,0'-diethylphosphorothio-S-acetyl-2-methyl-2(3-cyano-2-propyl) hydrazide (Compound 16) l-methyl-l(3-cyano-2-propy1)-2-chloroacetyl hydrazide was reacted withdiethylphosphorothioic acid ammonium salt to give an orange oil whichwas identified as 0,0- diethylphosphorothioS-acetyl-2-methyl-2(3-cyano-2-propyl)hydrazide. This was confirmed byNMR. The TLC was EtOH/EtOAc) R =0.32.

EXAMPLE 19 Preparation of 0,0'-dimethylphosphorothio-S-acetyl-2-methyl-Z-cyanomethyl hydrazide (Compound 17) 1methyl-1-cyanomethyl-2-chloroacetyl hydrazide was reacted withdimethylphosphorothioic acid ammonium salt to give an amber oil whichwas identified as 0,0- dimethylphosphorothio-S-acetyl2-methyl-2-cyanomethyl hydrazide. This structure was confirmed by NMR.The TLC was (BZ/EtOAc 50/50) R :0.94.

EXAMPLE 20 Preparation of 0,0-dimethylphosphorothio-S-acetyl-Z-methyl-2(3-cyano-2-propyl)hydrazide (Compound 18) 1-methyl-l(3-cyano 2propyl) 2 chloroacetyl hydrazide was reacted withdimethylphosphorothioic acid ammonium salt to give an amber oil whichwas identified as 0,0-dimethylphosphorothio-S-acetyl 2 methyl-2(3-cyano-Z-propyl)hydrazide. This structure was confirmed by NMR.

EXAMPLE 21 Preparation of 0,0'-dimethylphosphorothio-S-acetyl-2-methyl-2(2-ethoxyethyl)hydrazide (Compound 20) l-methyl-l(Z-ethoxyethyl)2 -chloroacetyl hydrazide was reacted with dimethylphosphorothioic acidammonium salt to give a black viscous oil which was identified as0,0-dimethylphosphorothio-S-acetyl 2 methyl-2(2- ethoxyethyDhydrazide.This structure was confirmed by NMR.

EXAMPLE 22 Preparation of 0,0-dimethylphosphorothio-S-acetyl 2-methyl-Z(N-methylcarboxamido)hydrazide (Compound 23) l-methyl-l(N-rnethylcarboxamido) 2 chloroacetyl hydrazide was reacted withdimethylphosphorothioic acid 20 ammonium salt to give a straw-coloredviscous oil which was identified as0,0'-dimethylphosphorothio-S-acetyl-2- methyl 2(N-methylcarboxamido)hydrazide. This structure was confirmed by NMR.

EXAMPLE 23 Preparation of 0,0'-dimethylphosphorothio-S-acetyl-Z-methyl-Z-carbothioethoxy hydrazide (Compound 24) l-methyl 1carbothioethoxy 2 chloroacetyl hydrazide was reacted withdimethylphosphorothioic acid ammonium salt to give a Straw-colored oilwhich was identified as 0,0'-dimethylphosphorothio S acety1-2-carbothioethoxy hydrazide. This structure was confirmed by NMR.

EXAMPLE 24 Preparation of 0,0-dimethylphosphorothio-S-acetyl-2-methyl-2-carboisopropoxy hydrazide (Compound 25)l-methyl-l-carboisopropoxy 2 chloroacetyl hydrazide was reacted withdimethylphosphorothioic acid ammonium salt to give an amber oil whichwas identified as 0,0-dimethylphosphorothio-S-acetyl 2mcthyl-Z-carboisopropoxy hydrazide. This structure was confirmed by NMR.

General experimental procedures for biological testing In the exampleswhich follow, the new thiophosphate esters were treated in thegreenhouse and in the laboratory to determine their biological activity.

The experimental compounds were tested as aqueous emulsions. Theseemulsions were prepared by dissolving the compound in acetone anddispersing it in distilled water with Triton X-100, an alkylarylpolyether alcohol derived by the reaction of i-octyl phenol withethylene oxide, to give spray emulsions containing the desiredconcentration of the compound. These emulsions were then used instandard laboratory tests described below.

Mexican bean beetle.Bean leaves were dipped in the emulsion of the testchemical and allowed to dry. The individual treated leaves were placedin Petri dishes and five Mexican bean beetle larvae introduced into eachof the two replicate dishes.

Mites, contact.Potted bean plants infested with the two-spotted spidermites were placed on a turntable and sprayed with a formulation of thetest chemical. The plants were held for seven days and the degree ofmite control was rated after this period.

Mites, systemic-Bean plants were treated by applying 20 ml. of theformulated test chemical to the soil. The mites were transferred to theplants after 24 hours. The plants were held for seven more days and thedegree of mite control rated.

Aphid, contact.Potted nasturtium plants infested with the bean aphidswere placed on a turntable and sprayed with a formulation of the testchemical. The plants were held for two days and the degree of aphidcontrol was rated.

Aphid, systemic.Nasturtium plants were treated by applying 20 ml. of theformulated test chemical to the soil. The mites were transferred to theplants after 24 hours. The plants were held for 48 additional hours andthe degree of the Aphid control rated.

Some of the compounds were also tested against other members ofcoleoptera order such as confused flour beetle and spider beetle, bollweevils as Well as adult Mexican bean beetles. They were also tested fortheir effectiveness to control German cockroaches and pea aphids. Testswere also done to determine their ovicidal action, and were activeagainst one or more of these species.

23 if R, and R are hydrogen, activity is very poor (note high LD s) Rand R should be alkyl or substituted alkyl or other substituents thanhydrogen.

(2) 0,0-diethylphosphorothio-S-acetyl 2 methyl-2-(2-cyanoethyl)hydrazide and Belgian Patent (A), within 240,0'-diethylphosphorothio-S-acetyl-Z-methyl-2-(2- ethoxyethyl hydrazide,0,0'-diethylphosph0rothio-S-(3-propionyl)-2-methyl-2-(2-cyanoethyl)hydrazide,O-ethyl-S-n-propylphosphorodithioS-acetyl-2-methy1- limits of error areequally active and very potent. 5 Z-(Z-cyanoethyl)hydrazide.

It was further found that the acute oral toxicity to rats0,0'-diethylphosphorothio-S-acetyl-Z-methyl-Z- of0,0-diethy1phosphorothio-s-acetyl 2 methyl-2-(2-(2-cyanoethyl)hydrazide, cyanoethyl)hydrazide and Belgian Patent (A) isvirtually 0,0'-diethylphosphorothio-S-(2-propionyl)-2-mcthylequal.2-(2-cyanoethyl)hydrazide, diethylphosphorothios acetyl 0,0-dimethylphosphorothio-S-acetyl-2-n1ethyl-2- 2 math 1 2(Z-cyanopropyl)hydrazide,

- y (2 cyanoethyl) 0,0 -diethylphosphorothro-S-acetyl-2-methyl-2-hydrazlde mg/kg' (3 cyano 2 propyl)hydrazide =2.1 k Bdglafl Patent (A)mg/ g 0,0'-d1methylphosphorothio-S-acetyl-2-methyl-2- Variation of thephosphate port1on resulted in the realcyanomethylhydrazide lzation thatthe dimethyl monothiophosphate moiety on h i S- 1.2- h pz- 3- 0cyano-2-propyl)hydrazide g 0,0-diethylphosphorothio-S- Z-ethylthioacetyl-2- 3 methyl-2-(cyanoethyl)hydrazide, lends the proper balance oftoxicity and insecticidal ac- O p s y 2 z tivity (Compounds 4 and 15,Table III) to the compounds (LethOXye-thyDhydmzida claimed in thispatent while the corresponding analog dimethylphosphoroth1o-S-acetyl-Z-methyl-Z- (Belgian PatentC, Table III) of theaforemennoned patcarbomethoxyhydrazidc, eat 15 very inactive.

TABLE III so (IMP-TIL) Mexican Mite Mite Mite Mite bean contact contactsystemic systemic Compound beetle adult nymph adult nymph CH1 p 5 4 10 54 cmom scmdnnn CHaCH CN Compound 4.

CH: 3 2 3 2 a (CflaOh l s CIIIPJNHN/ CH$HCN CH3 Compound 15.

CH! 250 130 260 so 130 (CIIa0)1i"s0H1( /NHN CH: Belgian Patent (0).

It was further found that Belgian Patent C decom-0,0'-dimethylphosphorothio-S-acetyl-2-methyl-2- posed fairly rapidlyupon standing whereas the com- (N-phenylcarboxamido)hydrazide, poundsclaimed in this patent are indeed stable and re- QOt i h wh h hi -S- 1-21-2 tain their activity. (N-methylearboxamido)hydrazide,

It was found that Compound 4 had an acute oral tox-OOgdimethylphosphomthio S acety1 2 methyl 2 icity of 46.4 mgJkg. andCompound 15 was 100 mg./ (carbothioethoxy)hydrazide, kg. These valuesmake the compounds more useful as OO, dimethylphosphorothio s acetyl 2melhyl 2 fii g iz carboisopropoxy hydrazide, and

1. A compound selected from the group consisting of g ig fz g ii'0,0'-diethylphosphorodithio-S-acetyl-2-methyl-2- 3 y) y raz e. l

(2 cyanoethy1) hydrazide, 2. A compound according to claim 1, which 1s0,0- 0,0-diethylphosphorothio-S-acetyl-2-methyl-2-dimethylphosQhorothio's'acetyl 2 methyl -PY phenyl-hydrazide, ethyl)hydraz1de. 0,0'-dimethylphosphorothio-S-acetyl-Z-methyl-Z- 3. A compoundaccording to claim 1, which is 0,0- (Z-cyanoethyl)-hydrazide,dimethylphosphorothio-S-acetyl 2 methyl-2-(2-cyano-0,0'-dimethylphosphorodithio-S-acetyl-Z-methylpropyl) hydrazide.

2-(2-cyanoethyl)hydrazide, 4. A compound according to claim 1, which is0,0- 0,0-diethylphosphorothio-S-acetyl-2-methyl-2-diethylphosphorothio-S(2-ethylthioacetyl) 2 methyl-2(2-cyanopropyl)hydrazide, (2-cyanoethyl hydrazide.0,0-diethylphosphorothio-S-acetyl-3-methyl-2-(2- 7 5. A compoundaccording to claim 1, which is 0,0- carboethoxyethyl)hydrazide,dimethylphosphorothio-S-acetyl-Z-methyl 2 carbome-0,0-diethylphosphorothio-S-acetyl-2-methyl-2- [2- thoxy hydrazide.

(N,N-dimethylcarboxamido)ethyl]hydrazide. 6. A compound according toclaim 1, which is 0,0- 0,0-diethylphosphorothio-S-acetyl-Z-methyl-Z-(2-dimethylphosphorothio-S-acetyl 2methyl-2(N-phenylmethylthioethyl)hydrazide, carboxamido) hydrazide.

7. A compound according to claim 1, which is 0,0-dimethylphosphorothio-S-acetyl 2 methyl-2 (N-methylcarboxamido)hydrazide.

8. A compound according to claim 1, which is 0,0-dimethylphosphorothio-S-acetyl 2 methyl-Z-carboisopropoxy hydrazide.

9. A compound according to claim 1, which is 0,0-diethylphosphorothio-S-acetyl 2 methyl 2 phenyl hydrazide.

10. A compound according to claim 1, which is 0,0- diethylphosphorothioS acetyl-Z-methyl 2(2-cyanopropyl) hydrazide.

11. A compound according to claim 1, which is 0,0- dimethylphosphorothioS acetyl 2 methyI-Z-cyanomethyl hydrazide.

UNITED STATES PATENTS 3,518,327 6/1970 Fearing 260-923 LEWIS GOTTS,Primary Examiner A. H. SU'I'IO, Assistant Examiner US. Cl. X.R.

